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HYDROXYANTHRAQUINONE DYES FROM
PLANTS
Yanis Caro, Thomas Petit, Isabelle Grondin, Mireille Fouillaud, Laurent
Dufossé
To cite this version:
Yanis Caro, Thomas Petit, Isabelle Grondin, Mireille Fouillaud, Laurent Dufossé.
HYDROXYAN-THRAQUINONE DYES FROM PLANTS. Symposium on natural colorants “Plants, Ecology and
Colours”, May 2017, Antananarivo, Madagascar. 2017. �hal-01518543�
skyrin
H
YDROXYANTHRAQUINONE
DYES
FROM
PLANTS
Yanis CARO
*,1, Thomas PETIT
2, Isabelle GRONDIN
1, Mireille FOUILLAUD
1and Laurent DUFOSSE
11 Laboratoire LCSNSA, Université de La Réunion (France); 2 UMR Qualisud, Université de La Réunion (France)
Introduc)on
In the plant kingdom, numerous pigments have already been iden)fied, but only a minority of them is allowed by legal regula)ons for texMle dyeing, food coloring or cosmeMc and pharmaceuMcs’ manufacturing. Anthraquinones, produced as secondary metabolites in plants, cons)tute a large structural variety of compounds among the quinone family. Anthraquinones are structurally built from an anthracene ring with a keto group on posi)on 9,10 as basic core and different func)onal groups such as -‐OH, -‐CH3, -‐
COOH, etc. may subs)tute at various posi)ons. Anthraquinones and their deriva)ves occur either in a free form (aglycone) or as glycosides. Hydroxyanthraquinone dyes usually refers to hydroxylated 9,10-‐ anthracenedione (from mono-‐, di-‐, tri-‐, up to octa-‐). They absorb visible light and are coloured (red, orange
and yellow). This work gives an overview on hydroxyanthraquinone dyes described in plants.
1) Plant sources of hydroxyanthraquinone dyes
About 700 natural hydroxyanthraquinone pigments have already been iden)fied from insects, lichens, filamentous fungi, or plants, and only few of them (f.i. carminic acid, Arpink red™, and alizarin from madder color) are already manufactured as natural colorants in tex)le, food, cosme)c or pharmaceu)cs industries. For example, fiQeen hydroxyanthraquinones’ deriva)ves from madder roots (Rubia Anctorum L., which contains 2-‐3.5 % pigments of dry weight) (CI Natural Red 8) play an important role in tex)le dyeing, prin)ng, and cosme)cs; but not in food in Europe or USA, even if it seems to have / had some uses in food in Japan (confec)onery, boiled fish, soQ drinks). Alizarin (Pigment Red 83, CI Mordant Red 11) is the main hydroxyanthraquinone dye in madder color. It is naturally bound to the disaccharide primeverose to build up the pigment ruberythric acid (yellow) in Rubiaceae. Purpurin (CI Natural Red 16) is a minor component in the madder color, but is the main dye in addi)on with munjisMn (orange-‐red crystals) in Indian madder (Rubia cordifolia). The color shades of madder color vary from scarlet, pink (high content of pseudopurpurin and/or purpurin, called pink madder or rose madder), carmine red (high content of alizarin), to red with a bluish )nt (alizarin lakes). Also oxida)ve coupling of two single hydroxyanthraquinones to form dimers (dianthrones) was found in plants, like the pharmaceu)cally used pigment hypericin from Hypericum species which is a dianthrone built up from two pigment emodin (yellow). Several other plant species, although producing hydroxyanthraquinones dyes are not considered viable contributors to the natural red dye market. This is the case of Anchusa )nctoria, Carthamus )nctoria,
Lithospermum spp. and Galium spp. Other plant species well-‐known as laxa)ves can produce hydroxyanthraquinone dyes like physcion, and they include senna
pods (Cassia angusAfolia), cascara sagrada (Rhamnus purshiana), frangula (Rhamnus frangula), rhubarb root (Rheum palmatum), yellow dock (Rumex crispus) and aloes (Aloe vera).
Fig.1: Main hydroxyanthraquinone natural dyes from plants
2) Nega)ve effects of hydroxyanthraquinone dyes
As hydroxyanthraquinone dyes are not yet widely applied, research work need to extend the knowledge concerning their potenMal roles onhuman health. Their posi)ve and/or nega)ve effects due to the 9,10-‐ anthracenedione structure and its subs)tuents are s)ll not clearly
understood and their poten)al role or effect on human health is currently being discussed by scien)sts.
For example, the roots of the european madder are rich in the highly colored, naturally occurring, glycosidic anthraquinoid compounds ruberythric acid, and lucidin-‐primeveroside. An intrinsic problem is the simultaneous hydrolysis of the glycoside lucidin-‐primeveroside to the
unwanted lucidin and rubiadin aglycones. Indeed, several toxicological
studies have concluded that rubiadin, lucidin, and more generally madder color, can induce carcinogenicity in rat kidney and liver, and they should be dealt carefully as a significant carcinogen against human (no data available for humans). Aloin from Aloe spp. also presents nega)ve effects on human diet.
References
1. Y Caro et al (2012), Natural hydroxyanthraquinoid pigments as potent food grade colorants: an overview. Natural Products & Bioprospecting, 2, p174-193. 2. N Sutthiwong et al (2013) Production of biocolours. In: Biotechnology in agriculture and food processing: opportunities and challenges, PS Panesar, SS Marwaha (Eds) 3. L Dufossé (2014), Anthraquinones, the Dr Jekyll and Mr Hyde of the food pigment family. Food Research International, 65, p.132-136
4. Y Caro et al (2015), Pigments and colorants from filamentous fungi. In: Fungal Metabolites (J-M Mérillon & KG Ramawat Eds.)
3) Posi)ve effects:
AnAtumor AcAvity and Cytotoxicity
Other well-‐known hydroxyanthraquinone dyes of natural origin and used as natural colorants (like carminic acid) are neither toxic nor known to be carcinogenic. Furthermore, numerous pharmacological studies have proved that some hydroxyanthraquinone dyes have biological posiMve
effects. Examples including emodin, aloe-‐emodin, rhein, physcion, purpurin, damnacanthal, which can inhibit the growth and proliferaMon of various cancer cells, such as lung adenocarcinoma, myelogenous
leukemia, neuroblastoma, hepatocellular carcinoma, bladder cancer, and others through cell death and survival’s modula)on.
Fig.2: Mutagen lucidin and rubiadin pigments from madder color
Conclusion
Finally, all these findings clearly indicate that hydroxyanthraquinone dyes of natural origin, such as from higher plants, might be considered as potent sources of novel an)cancer drugs and, at least, promising an)-‐leukemic agents, an)-‐invasive agents for human pancrea)c and gastric cancers chemotherapy, and an)tumor agents for hepatocellular carcinoma, bladder cancer, and others. However, the cytotoxicity caused by quinones in general is very complex and seems to occur through several mechanisms. Thus, due to differences in structures and characteris)cs among hydroxyanthraquinone dyes, and to the dose-‐dependant responses observed, the molecular mechanism of the toxicity of each pigment remains to be fully elucidated.
hypericin ruberythric acid emodin physcion rhein chrysophanol purpurin damnacanthal
Symposium/Festival on natural colorants “Plants, Ecology and Colours”
Antananarivo, Madagascar, 15 - 21 may 2017
H
YDROXYANTHRAQUINONE DYES FROM PLANTS
Yanis CARO
*,1
, Thomas PETIT
2
, Isabelle GRONDIN
1
,
Mireille FOUILLAUD
1
and Laurent DUFOSSE
1
1
Affiliation: Université de La Réunion, Laboratoire de Chimie des Substances Naturelles et des
Sciences des Aliments (LCSNSA), Réunion (France)
2
